A carbon nanotube can be visualized as a sheet of hexagonal graph paper rolled up into a seamless tube and joined. Each line on the graph paper represents a carbon—carbon bond, and each intersection point represents a carbon atom.
In general, carbon nanotubes are elongated tubular bodies which are typically only a few atoms in circumference. The carbon nanotubes are hollow and have a linear fullerene structure. The length of the carbon nanotubes potentially may be millions of times greater than their molecular-sized diameter. Both single-walled carbon nanotubes (SWNTs), as well as multi-walled carbon nanotubes (MWNTs) have been recognized.
Carbon nanotubes are currently being proposed for a number of applications since they possess a very desirable and unique combination of physical properties relating to, for example, strength and weight. Carbon nanotubes have also demonstrated electrical conductivity. See Yakobson, B. I., et al., American Scientist, 85, (1997), 324–337; and Dresselhaus, M. S., et al., Science of Fullerenes and Carbon Nanotubes, 1996, San Diego: Academic Press, pp. 902–905. For example, carbon nanotubes conduct heat and electricity better than copper or gold and have 100 times the tensile strength of steel, with only a sixth of the weight of steel. Carbon nanotubes may be produced having extraordinarily small size. For example, carbon nanotubes are being produced that are approximately the size of a DNA double helix (or approximately 1/50,000th the width of a human hair).
Considering the excellent properties of carbon nanotubes, they are well suited for a variety of uses, from the building of computer circuits to the reinforcement of composite materials, and even to the delivery of medicine. As a result of their properties, carbon nanotubes may be useful in microelectronic device applications, for example, which often demand high thermal conductivity, small dimensions, and light weight. One potential application of carbon nanotubes that has been recognized is their use in flat-panel displays that use electron field-emission technology (as carbon nanotubes can be good conductors and electron emitters). Further potential applications that have been recognized include electromagnetic shielding, such as for cellular telephones and laptop computers, radar absorption for stealth aircraft, nano-electronics (including memories in new generations of computers), and use as high-strength, lightweight composites. Further, carbon nanotubes are potential candidates in the areas of electrochemical energy storage systems (e.g., lithium ion batteries) and gas storage systems.
Various techniques for producing carbon nanotubes have been developed. As examples, methods of forming carbon nanotubes are described in U.S. Pat. Nos. 5,753,088 and 5,482,601, the disclosures of which are hereby incorporated herein by reference. The three most common techniques for producing carbon nanotubes are: 1) laser vaporization technique, 2) electric arc technique, and 3) gas phase technique (e.g., HiPco™ process), which are discussed further below.
In general, the “laser vaporization” technique utilizes a pulsed laser to vaporize graphite in producing the carbon nanotubes. The laser vaporization technique is further described by A. G. Rinzler et al. in Appl. Phys. A, 1998, 67, 29, the disclosure of which is hereby incorporated herein by reference. Generally, the laser vaporization technique produces carbon nanotubes that have a diameter of approximately 1.1 to 1.3 nanometers (nm). Such laser vaporization technique is generally a very low yield process, which requires a relatively long period of time to produce small quantities of carbon nanotubes. For instance, one hour of laser vaporization processing typically results in approximately 100 milligrams of carbon nanotubes.
Another technique for producing carbon nanotubes is the “electric arc” technique in which carbon nanotubes are synthesized utilizing an electric arc discharge. As an example, single-walled nanotubes (SWNTs) may be synthesized by an electric arc discharge under helium atmosphere with the graphite anode filled with a mixture of metallic catalysts and graphite powder (Ni:Y;C), as described more fully by C. Joumet et al. in Nature (London), 388 (1997), 756. Typically, such SWNTs are produced as close-packed bundles (or “ropes”) with such bundles having diameters ranging from 5 to 20 nm. Generally, the SWNTs are well-aligned in a two-dimensional periodic triangular lattice bonded by van der Waals interactions. The electric arc technique of producing carbon nanotubes is further described by C. Journet and P. Bernier in Appl. Phys. A, 67, 1, the disclosure of which is hereby incorporated herein by reference. Utilizing such an electric arc technique, the average carbon nanotube diameter is typically approximately 1.3 to 1.5 nm and the triangular lattice parameter is approximately 1.7 nm. As with the laser vaporization technique, the electric arc production technique is generally a very low yield process that requires a relatively long period of time to produce small quantities of carbon nanotubes. For instance, one hour of electric arc processing typically results in approximately 100 milligrams of carbon nanotubes.
More recently, Richard Smalley and his colleagues at Rice University have discovered another process, the “gas phase” technique, which produces much greater quantities of carbon nanotubes than the laser vaporization and electric arc production techniques. The gas phase technique, which is referred to as the HiPco™ process, produces carbon nanotubes utilizing a gas phase catalytic reaction. The HiPco process uses basic industrial gas (carbon monoxide), under temperature and pressure conditions common in modem industrial plants to create relatively high quantities of high-purity carbon nanotubes that are essentially free of by-products. The HiPco process is described in further detail by P. Nikolaev et al. in Chem. Phys. Lett., 1999, 313, 91, the disclosure of which is hereby incorporated herein by reference.
While daily quantities of carbon nanotubes produced using the above-described laser vaporization and electric arc techniques are approximately 1 gram per day, the HiPco process may enable daily production of carbon nanotubes in quantities of a pound or more. Generally, the HiPco technique produces carbon nanotubes that have relatively much smaller diameters than are typically produced in the laser vaporization or electric arc techniques. For instance, the nanotubes produced by the HiPco technique generally have diameters of approximately 0.7 to 0.8 nm.
Molecular engineering (e.g., cutting, solubilization, chemical functionalization, chromatographic purification, manipulation and assembly) of single-walled carbon nanotubes (SWNTs) is expected to play a vital role in exploring and developing the applications of carbon nanotubes. Noncovalent functionalization of carbon nanotubes has received particular growing interest recently, because it offers the potential to add a significant degree of functionalization to carbon nanotube surfaces (sidewalls) while still preserving nearly all of the nanotubes' intrinsic properties. For example, SWNTs can be solubilized in organic solvents and water by polymer wrapping (see e.g., (a) Dalton, A. B.; et al. J. Phys. Chem. B 2000, 104, 10012–10016; (b) Star, A.; et al. Angew. Chem., Int. Ed. 2001, 40, 1721–1725; (c) O'Connell, M. J.; et al. Chem. Phys. Lett. 2001, 342, 265–271; and published U.S. patent Application Numbers 2002/0046872, 2002/0048632, and 2002/0068170 by Richard E. Smalley, et al., each titled “POLYMER-WRAPPED SINGLE WALL CARBON NANOTUBES”), and nanotube surfaces can be noncovalently functionalized by adhesion of small molecules for protein immobilization (see e.g., Chen, R. J.; et al. J. Am. Chem. Soc. 2001, 123, 3838–3839).
Full-length (unshortened) carbon nanotubes, due to their high aspect ratio, small diameter, light weight, high strength, high electrical- and thermal-conductivity, are recognized as the ultimate carbon fibers for nanostructured materials. See Calvert, P. Nature 1999, 399, 210, and Andrews, R. et al. Appl. Phys. Lett. 1999, 75, 1329, the disclosures of which are hereby incorporated herein by reference. The carbon nanotube materials, however, are insoluble in common organic solvents. See Ebbesen, T. W. Acc. Chem. Res. 1998, 31, 558–556, the disclosure of which is hereby incorporated herein by reference.
Covalent side-wall functionalizations of carbon nanotubes can lead to the dissolution of carbon nanotubes in organic solvents. It should be noted that the terms “dissolution” and “solubilization” are used interchangeably herein. See Boul, P. J. et al., Chem Phys. Lett. 1999, 310, 367 and Georgakilas, V. et al., J. Am. Chem. Soc. 2002, 124, 760–761, the disclosures of which are hereby incorporated herein by reference. The disadvantage of this approach is that a carbon nanotube's intrinsic properties are changed significantly by covalent side-wall functionalizations.
Carbon nanotubes can also be solubilized in organic solvents and water by polymer wrapping. See Dalton, A. B. et al., J. Phys. Chem. B 2000, 104, 10012–10016, Star, A. et al. Angew. Chem., Int. Ed. 2001, 40, 1721–1725; O'Connell, M. J. et al. Chem. Phys. Lett. 2001, 342, 265–271; and published U.S. Patent Application Numbers 2002/0046872, 2002/0048632, and 2002/0068170 by Richard E. Smalley, et al., each titled “POLYMER-WRAPPED SINGLE WALL CARBON NANOTUBES”, the disclosures all of which are hereby incorporated herein by reference. FIGS. 1A–1C show examples of such polymer wrapping of a carbon nanotube. In polymer wrapping, a polymer “wraps” around the diameter of a carbon nanotube. For instance, FIG. 1 shows an example of polymers 102A and 102B wrapping around single-walled carbon nanotube (SWNT) 101. FIG. 1B shows an example of polymer 103A and 103B wrapping around SWNT 101. FIG. 1C shows an example of polymers 104A and 104B wrapping around SWNT 101. It should be noted that the polymers in each of the examples of FIGS. 1A–1C are the same, and the FIGURES illustrate that the type of polymer-wrapping that occurs is random (e.g., the same polymers wrap about the carbon nanotube in different ways in each of FIGS. 1A–1C).
One disadvantage of this approach is that the polymer is very inefficient in wrapping the small-diameter single-walled carbon nanotubes produced by the HiPco process because of high strain conformation required for the polymer. For example, such polymer wrapping approach can only solubilize the SWNTsHiPco (i.e., SWNTs produced by the HiPco process) at about 0.1 mg/ml in organic solvents. SWNTHiPco is the only SWNT material that can be currently produced at a large scale with high purity. Further, polymer-wrapping offers no control over the spacing of functional groups that may be arranged along the polymer. That is, as the polymer wraps around a nanotube, which as the examples of FIGS. 1A–1C illustrate may be in a random manner, the spacing of functional groups that may be included on the polymer is uncontrolled.